JPH05241015A - Thin film manufacturing method and color filter manufacturing method using the same - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a method for producing a thin film having a uniform film thickness and free from color spots and irregularities, and a method for producing a color filter using the method. [Structure] An electrode-forming substrate is inserted into a dispersion or micellar electrolyte obtained by dispersing or solubilizing a hydrophobic substance in an aqueous medium using a surfactant made of a ferrocene derivative, and the electrodes on the substrate are energized. In the method for producing a thin film in which a thin film of a hydrophobic substance is processed to form a rectangular wave,
Electrolysis is performed by applying a periodically changing voltage or current to the electrodes, which has at least one waveform selected from a trapezoidal wave, a triangular wave, a sine wave, and a sawtooth wave, or a composite waveform of these waveforms.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thin film and a method for producing a color filter using this method.

[0002]

2. Description of the Related Art As a method for producing a thin film such as a dye layer of a color filter, a printing method of printing inks of RGB three primary colors on a glass substrate using a printing machine, an ultraviolet curable resist in which pigments are dispersed is usually used. RG is applied on a glass substrate and masked by photolithography and heat-cured.
B: Dispersion method for forming a dye layer repeatedly three times, a resist method as a dye-preventing film is formed on gelatin by a photolithography method, a dyeing method for dyeing each of RGB colors with a dye, an electrodeposition polymer and a pigment are dispersed, and a substrate is formed. Known are the electrodeposition method of performing electrodeposition coating using the electrode formed above, and the micelle electrolysis method of performing electrolysis using the electrode formed on a substrate by dispersing a surfactant and a pigment. ..

Of these, the micelle electrolysis method (Japanese Patent Laid-Open No. 63-24329)
(See JP No. 8), a micelle agent composed of a ferrocene derivative and a coloring material (hydrophobic coloring matter) are added to an aqueous medium in which a supporting electrolyte or the like is added to water to adjust the electric conductivity, as necessary. When mixed and stirred to disperse, micelles having the dye material incorporated therein are formed. Then, when this is subjected to electrolytic treatment, the micelle is attracted to the anode and the ferrocene derivative in the micelle loses the electron e ⁻ on the anode (transparent electrode) (Fe ^{2+ in} ferrocene is oxidized to Fe ³⁺ ),
At the same time, the micelles collapse and the dye material inside breaks out on the anode to form a thin film. On the other hand, the oxidized ferrocene derivative is attracted to the cathode to receive the electron e ⁻ ,
Form micelles again. In the process of repeated formation and disintegration of such micelles, particles of the dye material are projected on the transparent electrode to form a thin film, and a desired dye thin film is formed.

[0004]

However, in the above-described conventional method for producing a thin film or a color filter by the micelle electrolysis method, when electrolysis is performed using patterned electrodes, for example, stripe-shaped or mosaic-shaped electrodes. However, since a constant potential is simply applied to the target electrode, natural convection of the electrolytic solution determines the deposition rate of the pigment thin film, resulting in a film thickness distribution in the pigment thin film formed by electrolysis, resulting in an uneven film thickness. become. For this reason, there is a problem in that the pigment thin film has dark and light spots (color spots), and smoothness is lost due to the unevenness of the film surface.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a method for manufacturing a thin film having a uniform film thickness and free from color spots and unevenness, and a method for manufacturing a color filter using this method. And

[0006]

In order to achieve the above object, the method for producing a thin film of the present invention is obtained by dispersing or solubilizing a hydrophobic substance in an aqueous medium using a surfactant comprising a ferrocene derivative. In the method of manufacturing a thin film, in which the electrode-forming substrate is inserted into the dispersion liquid or the micelle electrolytic solution, and the electrodes on the substrate are energized to form a thin film of a hydrophobic substance on the electrode, a voltage or current that changes periodically. Is applied to the electrodes to perform electrolysis, and it is preferable that the periodically changing voltage or current applied to the electrodes is at least one selected from a rectangular wave, a trapezoidal wave, a triangular wave, a sine wave, and a sawtooth wave. Waveform or a composite waveform of these waveforms, and when conducting current to the electrodes on the substrate, the potential other than the redox potential of the ferrocene derivative surfactant is applied to electrodes other than the target electrode for electrolysis. It is constituted to be applied.

Further, the method for producing a color filter of the present invention uses a surfactant made of a ferrocene derivative to produce a red,
Substrate for producing a color filter in which a patterned transparent electrode is formed in each of a dispersion or a micellar electrolyte obtained by dispersing or solubilizing a pigment or dye having spectral characteristics of three primary colors of green and blue in an aqueous medium. In the method for manufacturing a color filter in which a transparent thin film on the substrate is energized and a dye thin film is formed on the transparent electrode.
Electrolysis is performed by applying a periodically changing voltage or current to the transparent electrode, and preferably, the periodically changing voltage or current applied to the electrode is a rectangular wave, a trapezoidal wave,
At least one waveform selected from a triangular wave, a sine wave, and a sawtooth wave, or a composite waveform of these waveforms is used, and when a transparent electrode on a substrate is energized, a ferrocene derivative is applied to a transparent electrode other than the target electrode for electrolysis. This is a method of applying a potential lower than the redox potential of the surfactant.

The present invention will be described in detail below. FIG. 1 is a diagram showing a manufacturing process of a thin film of the present invention. The method of manufacturing the color filter of the present invention using the method of manufacturing the thin film of the present invention will also be described.

In the method for producing a thin film of the present invention, a dispersion or micellar electrolytic solution obtained by dispersing or solubilizing a hydrophobic substance in an aqueous solvent using a surfactant made of a ferrocene derivative is used.

(1) The ferrocene derivative surfactant (micelling agent) can extremely efficiently disperse or solubilize a hydrophobic substance in an aqueous medium. Here, there are various types of ferrocene derivatives.

[0011]

[Chemical 1] [Wherein R ¹ and R ² are each an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an amino group, a dimethylamino group, a hydroxyl group, an acetylamino group, a carboxyl group, a methoxycarbonyl group, an acetoxy group, Represents an aldehyde group or halogen, R ³ is hydrogen or has 4 to 4 carbon atoms
18 linear or branched alkyl or alkenyl groups, R ⁴ and R ⁵ each represent hydrogen or methyl group, Y represents oxygen, oxycarbonyl group or acyloxy group, a represents an integer of 0 to 4, b Is an integer from 0 to 4, m
Is an integer of 1 to 18 and n is a real number of 2.0 to 70.0] as a representative example (Japanese Patent Application No. 1-24108).

(2) As the hydrophobic substance, for example, red,
Examples include hydrophobic dye pigments such as green, blue, and black. Here, as the hydrophobic red dye pigment, for example, perylene pigments, lake pigments, azo pigments, diazo pigments, quinacridone pigments, anthraquinone pigments, dianthraquinone pigments or anthracene pigments, and the like, more specifically Is a perylene pigment, a lake pigment (Ca, Ba, S
r, Mn), quinacridone, naphthol AS, shicomin pigment, anthraquinone (Sudan I, II, III, R), disazo, benzopyran, cadmium sulfide pigment, Fe (II
I) Oxide pigments, etc. As the hydrophobic green dye pigment, there are halogen polysubstituted phthalocyanine pigments, halogen polysubstituted copper phthalocyanine pigments, triphenylmethane basic dyes and the like, and more specifically, chloro polysubstituted phthalocyanines, copper complexes thereof or Examples include barium-triphenylmethane dye. Examples of the hydrophobic blue pigment include copper phthalocyanine pigment, indanthrone pigment, indophenol pigment, and cyanine pigment, and more specifically, chlorocopper phthalocyanine, chloroaluminum phthalocyanine, vanadic acid phthalocyanine, and magnesium phthalocyanine. , Phthalocyanine metal complexes such as zinc phthalocyanine, iron phthalocyanine and cobalt phthalocyanine, phthalocyanine, merocyanine or indophenol blue.

In the case of producing a color filter, a dianthraquinone pigment is used as a red pigment, a bromo / chlorocopper phthalocyanine pigment and an isoindolinone mixed pigment are used as a green pigment, and a copper phthalocyanine pigment and a dioxazine pigment are used as blue pigments. It is preferable to use a mixed pigment or the like.

(3) Next, the above-mentioned ferrocene derivative surfactant (micelling agent), a hydrophobic substance and, if necessary, a supporting salt are added to an aqueous medium, and these are mixed, and then ultrasonic waves (homogenizer) or A stirrer such as a stirrer is sufficiently dispersed to form micelles, and then excess dye material is removed as necessary to obtain a micelle solution (or dispersion).

At this time, the concentration of the Fersen derivative surfactant may be at least the limit micelle concentration (0.1 mM), but is preferably about 2.0 mM. The concentration of the hydrophobic substance may be equal to or higher than the saturation concentration, for example, 1
~ 100 g / l.

The supporting salt (supporting electrolyte) is added as necessary in order to adjust the electric conductivity of the aqueous medium. The amount of the supporting salt added may be in a range that does not prevent precipitation of the solubilized or dispersed dye material, and the concentration is usually about 0.05 to 200 mM. Electrolysis can be performed without adding the supporting salt, but in this case, a highly pure thin film containing no supporting salt is obtained. Further, when a supporting salt is used, the type of the supporting salt is not particularly limited as long as it can control the electric conductivity of the aqueous medium without hindering the formation of micelles or the deposition of the dye material on the electrode. .. Specifically, sulfates (salts of lithium, potassium, sodium, rubidium, aluminum, etc.) and halides (lithium, potassium, sodium, rubidium, etc.) which are generally widely used as supporting salts,
Salts of calcium, magnesium, aluminum, etc.),
Ammonium salt (salt such as boron tetrafluoride) Water-soluble oxide salt (lithium, potassium, sodium, rubidium,
Salts of calcium, magnesium, aluminum, etc.),
Acetate salts (salts of lithium, potassium, sodium, rubidium, beryllium, magnesium, calcium, strontium, barium, aluminum, etc.) are preferred.

(4) Next, the electrode forming substrate is inserted into the micelle electrolyte solution (or dispersion solution) prepared as described above. Here, the electrode forming substrate is not particularly limited as long as the electrode is formed on the substrate, and the electrode pattern is not particularly limited. Examples of the electrode forming substrate include platinum, gold, carbon, or a substrate for producing a color filter in which a transparent electrode for forming a dye layer (ITO electrode) is formed on a transparent glass substrate.

(5) After inserting the electrode-forming substrate into the micellar electrolytic solution (or dispersion), the electrodes on the substrate are energized for electrolysis to form a thin film of a hydrophobic substance on the electrode (FIG. 3). ..

In the method of the present invention, during this electrolysis,
It is characterized in that electrolysis is performed by applying a voltage or current that changes periodically to the electrodes. That is, the voltage or current applied to the electrodes during electrolysis is not a constant voltage or a constant current,
The voltage or current is periodically changed to carry out electrolysis while controlling the electrolysis conditions.

As the voltage or current which changes periodically,
As shown in FIGS. 2A to 2E, a rectangular wave (pulse wave)
(FIG. 2 (a)), trapezoidal wave (FIG. 2 (b)), triangular wave (FIG. 2)
(C)), sine wave (Fig. 2 (d)), sawtooth wave (Fig. 2 (e))
And so on. These waveforms may be used alone or as a composite waveform of two or more types.

When a rectangular wave pulse is used as the voltage or current which changes periodically, for example, the pulse width a is set to 0.
01 to 5 seconds, the interval b between pulses is 0.05 to 30 seconds, and the pulse height c is 0.3 to 1.5 V or 10 μA.
˜1 mA / cm ^2, and bias (voltage or current) d is 0 to 0.25 V or 0 to 100 μA / cm ² . The temperature of the electrolytic solution is 0 to 90 ° C, preferably 20 to 70 ° C. To generate a cyclically changing voltage or current,
For example, as shown in FIG. 3, the function generator 15 is provided on the potentiostat 14 which is connected to the electrode 1, the sweet candy electrode (SCE) 12 and the counter electrode 13 on the electrode forming substrate 10, respectively.
Should be connected.

As described above, by performing electrolysis by using the voltage or current which changes periodically, the film forming rate of the thin film formed on the electrode is not affected by natural convection of the electrolytic solution. The film-forming speed is determined only by the concentration gradient of the hydrophobic substance, and the film thickness is uniform over the entire surface of the substrate, and a thin film with less color spots and unevenness can be obtained.

During electrolysis, as shown in FIG. 4, it is preferable to apply a potential equal to or lower than the redox potential of the ferrocene derivative surfactant to electrodes other than the target electrode for electrolysis. Specifically, in addition to the potentiostat 14 used for electrolysis of the target electrode, the potentiostat 16
Is provided, and this is connected to an electrode other than the target electrode, and a potential lower than the redox potential of the ferrocene derivative surfactant is applied. By doing so, as shown in Examples 6 to 10 of Table 1 and Example 16 of Table 2, thin films with few white spots can be obtained.

For example, in the manufacture of a color filter, micelle electrolytes of RGB colors are used on red (R), green (G) and blue (B) dye forming electrodes (mosaic or stripe). , A dye thin film is formed for each of the RGB colors. During this electrolysis, a potential equal to or lower than the redox potential of the ferrocene derivative surfactant is applied to the two-color electrodes other than the one-color target electrode for electrolysis.

(6) After the thin film is formed by the above electrolysis, washing with pure water or electrolytic washing is performed to remove the electrolytic solution, and then baking is performed to complete the thin film. In the case of manufacturing a color filter, after washing with pure water, electrolytic washing, and washing with a conductivity adjusting liquid (for example, E = −0.8 V.vs SCE for 3 minutes), it is dried with warm water and post-baked (for example, 100 ° C.,
For 15 minutes) to complete the dye thin film.

(7) In the case of manufacturing a color filter, after forming the dye layer, a protective film (smooth film or top coat film) is formed thereon. The protective film is formed by spin-coating or roll-coating a polymer such as a top coat agent and then post-baking this. Here, examples of the top coat agent include acrylic resins, polyester resins, polyolefin resins, phosphazene resins, polyphenylene sulfide resins, and the like. An ITO thin film or a conductive thin film layer of tin oxide or the like is formed on the protective film. The conductive thin film such as the ITO film is formed by a sputtering method, a vapor deposition method, a biosol method or the like. The ITO thin film or the like is patterned by a photolithography method to form a liquid crystal driving electrode (rear ITO electrode).
The patterning of the ITO thin film by the photolithography method includes (a) resist coating, (b) exposure, (c) development,
(D) The etching of the ITO thin film and (e) the resist peeling are performed in this order. An RGB color separation color filter by the micelle electrolysis method is manufactured through the above-described process.

The above-described color filter of the present invention is a color liquid crystal display such as a personal computer, a word processor, a wall-mounted TV, a pocket liquid crystal TV, an auroraviation, a color filter such as a solid-state image sensor (CCD), an audio, an in-vehicle instrument panel, It is preferably used in the fields of color displays such as clocks, calculators, VCRs, fax machines, communication devices, games and measuring instruments.

[0028]

The present invention will be described in more detail based on the following examples. Example 1 Formation of ITO electrode (electrode for forming dye layer) A glass substrate having a sheet resistance of 20Ω / □ as an ITO film (Matsuzaki Vacuum Co., Ltd .: soda lime glass, surface polishing, silica dip product) was applied with an ultraviolet curable resist agent. (Fuji Hunt Electronics Technology Co., Ltd .: IC-28 / T3) is diluted twice with xylene, and a solution is spin-coated at a rotation speed of 1000 rpm. After spin coating, prebaking is performed at 80 ° C. for 15 minutes. After that, this resist / ITO
The film substrate is set in the exposure device. The mask has a line width of 100μ
m / gap 20 μm, line length 230 mm, number 1920
The vertical stripe pattern of the book. A 2 kw high-pressure mercury lamp (exposure intensity: 10 mw / cm ² ) is used as a light source. The proximity gap is set to 70 μm, and after exposure for 60 seconds, development is performed with a developing solution. After development, rinse with pure water and post-baking at 180 ° C. Next, as an etchant, 1N FeCl ₃ · 1N HCl · 0.1N
An aqueous solution of HNO ₃ .0.1N Ce (NO ₃ ) ₄ is prepared, and the ITO film is etched. The end of etching was determined by measuring electric resistance. This etching required about 20 minutes. After etching, rinse with pure water and strip the resist with 1N NaOH. The ITO patterned glass substrate is obtained as described above.

Formation of resist black matrix As a resist agent for forming a black matrix, a color mosaic C manufactured by Fuji Hunt Electronics Technology Co., Ltd.
A mixture of K, CR, CG, and CB in a weight ratio of 3: 1: 1: 1 is used. The ITO patterned glass substrate prepared in the previous step is rotated at 10 rpm, and 30 cc of the resist agent is sprayed onto the rotated substrate. Next, the rotation speed of spin coating is set to 2,500 rpm, and the resist is uniformly coated (formed) on the substrate. After coating, the substrate is pre-baked at 80 ° C for 15 minutes. Then, while aligning with an aligner having an alignment function, exposure is carried out using a black matrix and a design mask (90 × 310 mm square, 20 mm line width) for forming an electrode extraction window. A 2 kw high-pressure mercury lamp is used as a light source (light amount: 100 mJ / cm ² ). After making the proximity gap 70 μm and exposing for 200 seconds, it is developed with an alkali developing solution. After electrolysis for 20 minutes, a developing solution (Fuji Hunt Electronics Technology Co .: C
D) is diluted with pure water four times and developed for 30 seconds. Further, it is rinsed with pure water and post-baked at 200 ° C. for 100 minutes. Silver paste (manufactured by Tokuriki Kagaku: P-28)
0) is applied to the electrode extraction window frame using a dispenser,
After connecting each R (red) row, B (blue) row, and G (green) row of electrodes, baking is performed at 150 ° C. for 100 minutes. By the above,
An insulating protective film is formed on a portion other than the effective display portion on the substrate, and at the same time, an electrode extraction window frame is formed.

Dye film formation Ferrocene derivative micelle agent FPE in 4 liters of pure water
G (Dojindo Co., Ltd.) 2 mM, LiBr (Wako Pure Chemical Industries, Ltd.)
0.1 M and 10 g / l of a dianthraquinone pigment (manufactured by Sanyo Dye Co., Ltd.) as a red pigment were added and dispersed with an ultrasonic homogenizer for 30 minutes to prepare a micelle solution, and then the above I
A TO patterning glass substrate is inserted into the micelle solution, and a potentiostat with an external function generator is connected to the R row of the stripe. The voltage applied to the electrodes during this electrolysis is the rectangular wave (a: 0.3) shown in FIG.
Sec, b: 6 seconds, c: 0.5 V, d: 0.2 V). After electrolysis for 20 minutes, it is washed with pure water and prebaked (120 ° C.) in an oven. In G, chlorinated brominated phthalocyanine-based green pigment and isoindolinone-based yellow pigment were used instead of the red pigment in separate pure water.
Micelle solutions were prepared in the same manner as in R except that they were added at a concentration of 5 g / l, and then the respective micelle solutions were mixed at a ratio of 7: 3 to form a film under the same conditions as the film formation for R. ..
The conditions of electrolysis such as applied voltage and the post-treatment after electrolysis are the same as in the case of R. In B, a micelle solution was prepared in the same manner as in R film forming, except that a phthalocyanine blue pigment and a dioxazine purple pigment were added to separate pure water at a concentration of 10.9 g / l instead of the red pigment. Later, 7: 3
The micelle solutions are mixed in the respective ratios, and film formation is performed under the same conditions as the R film formation. The conditions of electrolysis such as applied voltage and the post-treatment after electrolysis are R cases. By the above electrolysis operation, RG
A B color filter dye thin film is obtained.

Formation of Protective Film The dye thin film forming substrate is set on a spin coater, and OS-808 (Nagase Sangyo Co., Ltd.) as a flat film agent is applied using a dispenser. The substrate is rotated at 10 rpm to apply it evenly over the entire substrate. Further, it is rotated at 800 rpm for 2 minutes to obtain a uniform thin film. Then, it is baked and cured at 260 ° C. for 2 hours. The STN having the protective film formed as described above
Get RGB color filter for.

[0032] was carried out measuring physical properties of a color filter fabricated by measurements of physical properties above steps. A spectrophotometer (MCPD-
1100, manufactured by Otsuka Electronics Co., Ltd.) was used. The transmittance of the glass substrate was standardized to 100%, and the transmittance of ITO / pigment thin film / protective film was used for evaluation. 450 for each RGB
The transmittance was evaluated for wavelengths of nm, 545 nm, and 610 nm. RGB stains are generated by contaminating each color electrode with an electrolyte solution other than the intended color. The stain evaluation (stain rate) was evaluated by the difference between the transmittance of the color filter manufactured here and the transmittance of Comparative Examples 2 to 4. For the white spot ratio, see the optical microscope (40
After taking a photograph at (0 times), the ratio of the blank area to the pixel area was evaluated as the blank ratio. For the evaluation of spots, the chromaticity of 9 pixels on the substrate is measured for each RGB,
The color difference was evaluated as the largest (ΔE). The surface smoothness was measured using a surface unevenness measuring device (Dick Tuck).

Example 2 In the electrolysis operation of Example 1, potential waveforms (triangular waves) as shown in FIG. 2 (c) were applied to the R, G, and B film formations for 25 minutes. The results are shown in Table 1.

Example 3 In the electrolysis operation of Example 1, a potential waveform (trapezoidal wave) as shown in FIG. 2B was applied to the R, G, B film formation for 25 minutes. The results are shown in Table 1.

Example 4 In the electrolysis operation of Example 1, two potential waveforms (sawtooth waves) as shown in FIG.
It was applied for 5 minutes. The results are shown in Table 1.

Example 5 Regarding the electrolysis operation of Example 1, for the R, G, and B film formation, the amplitude was 0.25 V, the period was 5 seconds, and the lower potential was 0.
A sinusoidal waveform potential of 2 V and an upper potential of 0.7 V was applied for 20 minutes. The results are shown in Table 1.

Example 6 In the electrolysis operation of Example 1, 10 μA / cm ² (1 second) and 0 μA / cm ² for R, G, and B film formation, respectively.
A constant current pulse of cm2 (10 seconds) was applied for 20 minutes. The results are shown in Table 1.

Comparative Example 1 In the electrolysis operation of Example 1, a constant potential of 0.7 V was applied to the R, G, and B films for 10 minutes. The results are shown in Table 1.

Example 7 In the electrolytic operation of Example 1, F was applied to electrodes other than the target electrode.
The same operation as in Example 1 was performed except that 0.2 V was applied as a potential lower than the oxidation-reduction potential of PEG. The results are shown in Table 1.

Example 8 Regarding the electrolytic operation of Example 2, F was applied to electrodes other than the target electrode.
The same operation as in Example 2 was performed except that 0.2 V was applied as a potential lower than the oxidation-reduction potential of PEG. The results are shown in Table 1.

Example 9 In the electrolytic operation of Example 3, F was applied to electrodes other than the target electrode.
The same operation as in Example 3 was performed except that 0.2 V was applied as a potential lower than the oxidation-reduction potential of PEG. The results are shown in Table 1.

Example 10 Regarding the electrolytic operation of Example 4, F was applied to electrodes other than the target electrode.
The same operation as in Example 4 was performed except that 0.2 V was applied as a potential lower than the oxidation-reduction potential of PEG. The results are shown in Table 1.

Example 11 In the electrolytic operation of Example 5, F was applied to electrodes other than the target electrode.
The same operation as in Example 5 was performed except that 0.2 V was applied as a potential lower than the oxidation-reduction potential of PEG. The results are shown in Table 1.

Example 12 In the electrolytic operation of Example 6, F was applied to electrodes other than the target electrode.
The same operation as in Example 6 was performed except that 0.2 V was applied as a potential lower than the oxidation-reduction potential of PEG. The results are shown in Table 1.

Example 13 Regarding the electrolytic operation of Example 1, FES was used as a micellizing agent.
T (redox potential is shown in Table 3) was used at the same concentration,
The same operation as in Example 1 was performed. The results are shown in Table 1.

Example 14 Regarding the electrolysis operation of Example 1, FES was used as a micellizing agent.
The same evaluation as in Example 1 was performed except that T was used at the same concentration and a potential of 0.18 V, which was lower than the oxidation-reduction potential of FEST, was applied to the electrodes other than the target electrode. The results are shown in Table 1.
Shown in.

[0047]

[Table 1]

Example 15 Formation of chrome black matrix Alkali-free glass substrate (manufactured by HOYA: NA45 / 30)
A chromium (Cr) thin film having a thickness of about 2000 angstrom is deposited on a 0 mm square and a thickness of 1 mm by a sputtering method (SDP-550VT manufactured by ULVAC, Inc.) to form a thin film. On this Cr thin film, an ultraviolet curable resist agent (IC-28 / T3 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was added in an amount of 1.0.
Spin coat at a rotation speed of 00 rpm. After spin coating, prebaking is performed at 80 ° C. for 15 minutes. afterwards,
This resist / Cr / glass substrate is set in a stepper exposure machine (exposure intensity 10 mW / cm ² ) to perform exposure. The mask has a pixel size of 90 μm × as shown in FIG.
310 μm, line width 20 μm, effective area 160 mm x 1
Using a 55 mm grid pattern, one glass substrate is subjected to four step exposures. After exposure, develop and
Rinse with pure water and post bake at 150 ° C. Next, 1M as an etching liquid (etchant)
_{FeCl 3 · 1N HClO 4 · 0.1N} HNO 3 ·
An aqueous solution of 0.1N Ce (NO ₃ ) ₄ is prepared, and Cr on the substrate is etched. The end of etching was determined by measuring electric resistance. The etching required about 20 minutes. After etching, rinse with pure water and strip the resist with 1N NaOH. Wash thoroughly with pure water,
The chrome black matrix (BM) and the extraction electrode were completed.

Formation of Insulating Film and ITO Electrode Next, insulating silica (SiO ₂ ) (OCDTYPE-7 manufactured by Tokyo Ohka Kogyo Co., Ltd.) is spin-coated on the BM at a rotation speed of 1,000 rpm. After baking at 250 ° C. for 60 minutes, a sputtering apparatus (ULDP: SDP-
An ITO thin film is sputter deposited to a thickness of about 1,300 angstroms (550 VT). At this time, the substrate temperature was set to 200 ° C. in order to adjust the surface resistance of the ITO film to 20 Ω / □. This ITO thin film / CrB
M / UV-curable resist agent on glass substrate (Fuji Hunt Electronics Technology Co., Ltd .: IC-28 / T
3) is spin coated at a rotation speed of 1,000 rpm. After spin coating, prebaking is performed at 80 ° C. for 15 minutes. After that, this resist / ITO thin film / CrBM /
Contact exposure machine for glass substrate (exposure intensity: 10 mW /
cm ² ). A mask having a vertical stripe pattern with a line width of 92 μm, a gap of 18 μm, and a line length of 155 mm is used. A 2 kw high-pressure mercury lamp is used as a light source.
Proximity gap 50μ after alignment preparation
m, exposed for 15 seconds, and developed with an alkaline developer. After development, rinse with pure water and then 150 ℃
Post bake at. Next, 1M as an etchant
FeCl ₃ · 1N HCl · 0.1N HNO ₃ · 0.
Using 1N Ce (NO ₃ ) ₄ aqueous solution, IT on the substrate
The O thin film is etched to form an ITO electrode. The end of etching was determined by measuring electric resistance. The etching required about 20 minutes. After the etching is completed, the substrate is rinsed with pure water, and the resist is immersed and stripped with 1N NaOH. It is washed with pure water and it is confirmed that there is no electrical leak between adjacent ITO electrodes. This completed the ITO patterned glass substrate with BM.

Simultaneous formation of electrode extraction window frame An acrylic resist agent (CT manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is used as a resist agent for forming an electrode extraction window frame. The ITO patterned glass substrate with BM prepared above is rotated at 10 rpm, and 30 cc of the resist agent is sprayed thereon. Next, spin coating is performed at a rotation speed of 1,500 rpm to uniformly coat the substrate. After spin coating, the substrate is prebaked at 80 ° C. for 15 minutes. Then, after aligning with a contact exposure machine having a 20 kw high-pressure mercury lamp as a light source and having an alignment function, exposure is performed using a design mask for formation shown in FIG. Then, it is developed with a developing solution for 90 seconds, rinsed with pure water, and post-baked at 180 ° C. for 100 minutes. Through the above steps, the color filter manufacturing substrate is completed. Next, a silver paste (P-280, manufactured by Tokuriki Kagaku Co., Ltd.) was applied to the electrode extraction window frame using a dispenser, and each R
After connecting the (red) row, B (blue) row, and G (green) row, 15
Bake at 0 ° C for 100 minutes. By the above, the insulating protective film is formed on the portion other than the effective display portion on the substrate, and at the same time, the electrode extraction window frame is formed.

Formation of dye film Ferrocene derivative micelle agent FPE in 4 liters of pure water
G (Dojindo Co., Ltd.) 2 mM, LiBr (Wako Pure Chemical Industries, Ltd.)
0.1M and 10 g / l of red pigment dianthraquinone pigment (manufactured by Sanyo Dye Co., Ltd.) were added, and the mixture was mixed with an ultrasonic homogenizer to 3
After being dispersed for 0 minutes to form a micellar solution, the ITO patterned glass substrate is inserted into the micellar solution, and a potentiostat with an external function generator is connected to the R row of the stripe. The voltage applied to the electrodes during this electrolysis is the rectangular wave (a: 0.3 seconds, b: 6) shown in FIG.
Sec, c: 0.5 V, d: 0.2 V) is used. After electrolysis for 20 minutes, it is washed with pure water and prebaked (120 ° C.) in an oven. In G, a micellar solution was used in the same manner as in R, except that instead of the red pigment, a chlorinated brominated phthalocyanine green pigment and an isoindolinone yellow pigment were added in separate pure water at a concentration of 15 g / l. After preparing, the respective micelle solutions were mixed at a ratio of 7: 3, and the film was formed under the same conditions as the film formation of R. The conditions of electrolysis such as applied voltage and the post-treatment after electrolysis are the same as in the case of R. In B, a micellar solution was prepared in the same manner as in R film formation, except that a phthalocyanine-based blue pigment and a dioxazine-based purple pigment were added to separate pure water at a concentration of 10.9 g / l instead of the red pigment. After that, the micelle solutions are mixed at a ratio of 7: 3, and the film is formed under the same conditions as the R film formation. The conditions of electrolysis such as applied voltage and the post-treatment after electrolysis are the same as in the case of R. By the above electrolysis operation, RGB
Obtain a color filter dye film.

Formation of Protective Film The RGB color filter substrate obtained by the above process
It is rotated at 0 rpm, and 30 cc of JSS7265 top coat agent (Nippon Synthetic Rubber) is sprayed on this. Next, the rotation speed of spin coating was set to 1,000 rpm, and the substrate (R
It is evenly applied onto the GB color filter dye thin film).
After the spin coating is completed, post baking is performed under the conditions of 180 ° C. and 50 minutes. Through the above steps, an RGB color filter thin film for TFT is obtained.

Physical properties were measured in the same manner as in Example 1. The results are shown in Table 2.

Example 16 In Example 15, the same electrolysis operation as in Example 7 was performed. The results are shown in Table 2.

Comparative Example 4 In Example 15, the same electrolysis operation as in Comparative Example 1 was performed. The results are shown in Table 2.

Comparative Example 5 In Example 15, the same electrolysis operation as in Comparative Example 2 was performed. The results are shown in Table 2.

[0057]

[Table 2] As is clear from Table 1 and Table 2, the white spot ratio, the color spot (Δ
E), unevenness is better than the comparative example. The transmittances are the same.

[0058]

As described above, according to the method of manufacturing a thin film and the method of manufacturing a color filter of the present invention, it is possible to manufacture a thin film or a color filter having a uniform film thickness and no color spots or irregularities.

[Brief description of drawings]

FIG. 1 is a diagram showing a manufacturing process of a thin film of the present invention.

FIG. 2A to FIG. 2E are diagrams showing a mode of a voltage or a current that changes periodically.

FIG. 3 is a block configuration diagram for explaining an electrolysis step.

FIG. 4 is another block configuration diagram for explaining an electrolysis step.

FIG. 5 is a plan view showing a mask used in the manufacturing process of the color filter of the present invention.

FIG. 6 is a plan view showing another mask used in the manufacturing process of the color filter of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 ... Electrode formation substrate 11 ... Electrode 14, 16 ... Potentiostat 15 ... Function generator

[Table 3]

Claims (6)

[Claims] 1. An electrode-forming substrate is inserted into a dispersion liquid or a micelle electrolytic solution obtained by dispersing or solubilizing a hydrophobic substance in an aqueous medium using a surfactant made of a ferrocene derivative, and an electrode on the substrate. A method for producing a thin film, wherein a thin film of a hydrophobic substance is formed on an electrode by applying an electric current to the electrode, wherein a voltage or a current that changes periodically is applied to the electrode to carry out electrolysis. 2. The cyclically varying voltage or current applied to the electrode is at least one waveform selected from a rectangular wave, a trapezoidal wave, a triangular wave, a sine wave, and a sawtooth wave, or a composite waveform of these waveforms. Item 2. A method for producing a thin film according to Item 1. 3. When conducting electricity to the electrodes on the substrate,
3. The method for producing a thin film according to claim 1, wherein a potential lower than the redox potential of the ferrocene derivative surfactant is applied to electrodes other than the target electrode for electrolysis. 4. A dispersion or micellar electrolyte obtained by dispersing or solubilizing a pigment or dye having a spectral characteristic of the three primary colors of red, green and blue in an aqueous medium using a surfactant composed of a ferrocene derivative. In each method, a color filter manufacturing substrate in which patterned transparent electrodes are formed is sequentially inserted, and the transparent electrodes on the substrates are energized to form a dye thin film on the transparent electrodes. A method of manufacturing a color filter, characterized in that electrolysis is performed by applying a voltage or current that changes dynamically to a transparent electrode. 5. The cyclically changing voltage or current applied to the electrode is at least one waveform selected from a rectangular wave, a trapezoidal wave, a triangular wave, a sine wave, and a sawtooth wave, or a composite waveform of these waveforms. Item 4. A method for manufacturing a color filter according to item 4. 6. The electric potential lower than the redox potential of the ferrocene derivative surfactant is applied to a transparent electrode other than the target electrode for electrolysis when the transparent electrode on the substrate is energized. Item 4. A method for manufacturing a color filter according to item 4 or 5.